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Issue 23, 2019
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Core-crystalline nanoribbons of controlled length via diffusion-limited colloid aggregation

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Abstract

It has been previously reported that poly(ethylene) (PE)-based block copolymers self-assemble in certain thermosetting matrices to form a dispersion of one-dimensional (1D) nanoribbons. Such materials exhibit exceptional properties that originate from the high aspect ratio of the elongated nano-objects. However, the ability to prepare 1D assemblies with well-controlled dimensions is limited and represents a key challenge. Here, we demonstrate that the length of ribbon-like nanostructures can be precisely controlled by regulating the mobility of the matrix during crystallization of the core-forming PE block. The selected system to prove this concept was a poly(ethylene-block-ethylene oxide) (PE-b-PEO) block copolymer in an epoxy monomer based on diglycidyl ether of bisphenol A (DGEBA). The system was activated with a dual thermal- and photo-curing system, which allowed us to initiate the epoxy polymerization at 120 °C until a certain degree of conversion, stop the reaction by cooling to induce crystallization and micellar elongation, and then continue the polymerization at room temperature by visible-light irradiation. In this way, crystallization of PE blocks took place in a matrix whose mobility was regulated by the degree of conversion reached at 120 °C. The mechanism of micellar elongation was conceptualized as a diffusion-limited colloid aggregation process which was induced by crystallization of PE cores. This assertion was supported by the evidence obtained from in situ small-angle X-ray scattering (SAXS), in combination with differential scanning calorimetry (DSC) and transmission electron microscopy (TEM).

Graphical abstract: Core-crystalline nanoribbons of controlled length via diffusion-limited colloid aggregation

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Publication details

The article was received on 26 Mar 2019, accepted on 21 May 2019 and first published on 24 May 2019


Article type: Paper
DOI: 10.1039/C9SM00615J
Soft Matter, 2019,15, 4751-4760

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    Core-crystalline nanoribbons of controlled length via diffusion-limited colloid aggregation

    R. N. Schmarsow, M. Ceolín, I. A. Zucchi and W. F. Schroeder, Soft Matter, 2019, 15, 4751
    DOI: 10.1039/C9SM00615J

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